uu.seUppsala University Publications
Change search
Link to record
Permanent link

Direct link
BETA
Publications (10 of 10) Show all publications
Björklund, E. (2019). Avoiding ageing: Surface degradation of commercial electrode materials in lithium-ion batteries. (Doctoral dissertation). Uppsala: Acta Universitatis Upsaliensis
Open this publication in new window or tab >>Avoiding ageing: Surface degradation of commercial electrode materials in lithium-ion batteries
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The battery market today expands rapidly, not least for electric vehicles. But to compete against the combustion engine, the cost of batteries must be reduced. After years of usage, the batteries degrade and need to be exchanged, increasing the cost over the vehicle lifecycle. This can be mitigated by tailoring the usage conditions and the battery materials. Understanding and avoiding ageing can be key to a more sustainable transport system. This thesis contains studies on degradation processes in Li-ion batteries utilizing the LiNixMnyCozO2 (NMC) cathode material, and suggests strategies for the improvement of battery life time.

When cycling different negative electrodes – including graphite, lithium foil and lithium titanium oxide (LTO) – against NMC electrodes, only minor capacity fading was observed in the NMC-LTO and NMC-graphite cells, in contrast to the NMC-Li-metal cells. The capacity fading for Li-metal cells was determined to be caused by degradation products formed at the lithium foil which thereafter diffused to the NMC electrode, leading to a higher resistance. Commercial NMC/LiMn2O4-graphite cells were also investigated after cycling in limited state of charge (SOC)-intervals. The cycle life was far longer in the low-SOC cell than in the high-SOC cell. Photoelectron spectroscopy revealed increased manganese dissolution in the high-SOC cell, likely causing a less stable solid electrolyte interphase layer on the negative electrode. This, in turn, limits the capacity. How temperature influence ageing in NMC-LTO was analysed in cells cycled at -10 °C, 30 °C and 55 °C. It was found that the initial side reactions at the LTO electrode limited the cell capacity, but that these also stabilized the NMC electrode. At 55 °C, excessive side reactions at LTO caused capacity fading due to loss of active lithium. At -10 °C, high cell resistance limited the capacity. Switching to a PC based electrolyte allowed stable low temperature cycling, although it was found that PC degraded and formed thick electrode surface layers. Also sulfolane-based electrolytes were investigated, showing thinner surface layers than the EC containing reference electrolyte at high potentials, thus indicating a more stable electrolyte system.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2019. p. 72
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1802
Keywords
Li-ion battery, Ageing, Photoelectron spectroscopy, Nickel Manganese Cobalt Oxide
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-381548 (URN)978-91-513-0639-1 (ISBN)
Public defence
2019-06-05, Room 4001, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2019-05-09 Created: 2019-04-11 Last updated: 2019-06-17
Naylor, A. J., Makkos, E., Maibach, J., Guerrini, N., Sobkowiak, A., Björklund, E., . . . Bruce, P. G. (2019). Depth-dependent oxygen redox activity in lithium-rich layered oxide cathodes. Journal of Materials Chemistry A, 7(44), 25355-25368
Open this publication in new window or tab >>Depth-dependent oxygen redox activity in lithium-rich layered oxide cathodes
Show others...
2019 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, Vol. 7, no 44, p. 25355-25368Article in journal (Refereed) Published
Abstract [en]

Lithium-rich materials, such as Li1.2Ni0.2Mn0.6O2, exhibit capacities not limited by transition metal redox, through the reversible oxidation of oxide anions. Here we offer detailed insight into the degree of oxygen redox as a function of depth within the material as it is charged and cycled. Energy-tuned photoelectron spectroscopy is used as a powerful, yet highly sensitive technique to probe electronic states of oxygen and transition metals from the top few nanometers at the near-surface through to the bulk of the particles. Two discrete oxygen species are identified, On− and O2−, where n < 2, confirming our previous model that oxidation generates localised hole states on O upon charging. This is in contrast to the oxygen redox inactive high voltage spinel LiNi0.5Mn1.5O4, for which no On− species is detected. The depth profile results demonstrate a concentration gradient exists for On− from the surface through to the bulk, indicating a preferential surface oxidation of the layered oxide particles. This is highly consistent with the already well-established core–shell model for such materials. Ab initio calculations reaffirm the electronic structure differences observed experimentally between the surface and bulk, while modelling of delithiated structures shows good agreement between experimental and calculated binding energies for On−.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-399616 (URN)10.1039/C9TA09019C (DOI)000498556500014 ()
Available from: 2019-12-13 Created: 2019-12-13 Last updated: 2019-12-18Bibliographically approved
Björklund, E., Göttlinger, M., Edström, K., Brandell, D. & Younesi, R. (2019). Investigation of dimethyl carbonate and propylene carbonate mixtures for LiNi0.6Mn0.2Co0.2O2-Li4Ti5O12 cells. Chemelectrochem, 6(13), 3429-3436
Open this publication in new window or tab >>Investigation of dimethyl carbonate and propylene carbonate mixtures for LiNi0.6Mn0.2Co0.2O2-Li4Ti5O12 cells
Show others...
2019 (English)In: Chemelectrochem, E-ISSN 2196-0216, Vol. 6, no 13, p. 3429-3436Article in journal (Refereed) Published
Abstract [en]

It has recently been shown that ethylene carbonate (EC) experience poor stability at high potentials in lithium-ion batteries, and development of electrolytes without EC, not least using ethyl methyl carbonate (EMC), has therefore been suggested in order to improve the capacity retention. In this context, we here explore another alternative electrolyte system consisting of propylene carbonate (PC) and dimethyl carbonate (DMC) mixtures in NMC-LTO (LiNi0.6Mn0.2Co0.2O2, Li4Ti5O12) cells cycled up to 2.95 V. While PC experience wettability problems and DMC has difficulties dissolving LiPF6 salt, blends between these could possess complementary properties. The electrolyte blend showed superior cycling performance at sub-zero temperatures compared to EC-containing counterparts. At 30 degrees C, however, the PC-DMC electrolyte did not show any major improvement in electrochemical properties for the NMC-LTO cell chemistry. Photoelectron spectroscopy measurements showed that thin surface layers were detected on both NMC (622) and LTO electrodes in all investigated electrolytes. The results suggest that both PC and EC will react on the electrodes, but with EC forming thinner layers comprising more carbonates. Moreover, the electrochemical stability at high electrochemical potentials is similar for the studied electrolytes, which is surprising considering that most are free from the reactive EC component.

National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-381546 (URN)10.1002/celc.201900672 (DOI)000475512500026 ()
Funder
Swedish Energy Agency, 37725-1StandUp
Available from: 2019-04-11 Created: 2019-04-11 Last updated: 2019-08-19Bibliographically approved
Björklund, E., Naylor, A. J., Brant, W., Brandell, D., Younesi, R. & Edström, K. (2019). Temperature dependence of electrochemical degradation in LiNi1/3Mn1/3Co1/3O2/Li4Ti5O12 cells. Energy Technology, 7(9), Article ID 1900310.
Open this publication in new window or tab >>Temperature dependence of electrochemical degradation in LiNi1/3Mn1/3Co1/3O2/Li4Ti5O12 cells
Show others...
2019 (English)In: Energy Technology, ISSN 2194-4288, Vol. 7, no 9, article id 1900310Article in journal (Refereed) Published
Abstract [en]

Aging mechanisms in lithium‐ion batteries are dependent on the operational temperature, but the detailed mechanisms on what processes take place at what temperatures are still lacking. The electrochemical performance and capacity fading of the common cell chemistry LiNi1/3Mn1/3Co1/3O2 (NMC)/Li4Ti5O12 (LTO) pouch cells are studied at temperatures 10, 30, and 55 °C. The full cells are cycled with a moderate upper cutoff potential of 4.3 V versus Li+/Li. The electrode interfaces are characterized postmortem using photoelectron spectroscopy techniques (soft X‐ray photoelectron spectroscopy [SOXPES], hard X‐ray photoelectron spectroscopy [HAXPES], and X‐ray absorption near edge structure [XANES]). Stable cycling at 30 °C is explained by electrolyte reduction forming a stabilizing interphase, thereby preventing further degradation. This initial reaction, between LTO and the electrolyte, seems to be beneficial for the NMC–LTO full cell. At 55 °C, continuous electrolyte reduction and capacity fading are observed. It leads to the formation of a thicker surface layer of organic species on the LTO surface than at 30 °C, contributing to an increased voltage hysteresis. At 10 °C, large cell‐resistances are observed, caused by poor electrolyte conductivity in combination with a relatively thicker and LixPFy‐rich surface layer on LTO, which limit the capacity.

Keywords
aging, lithium-ion batteries, photoelectron spectroscopy
National Category
Energy Engineering Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-381545 (URN)10.1002/ente.201900310 (DOI)000483721900011 ()
Available from: 2019-04-11 Created: 2019-04-11 Last updated: 2019-12-09Bibliographically approved
Björklund, E., Wikner, E., Younesi, R., Brandell, D. & Edström, K. (2018). Influence of state-of-charge in commercial LiNi0.33Mn0.33Co0.33O2/LiMn2O4-graphite cells analyzed by synchrotron-based photoelectron spectroscopy. Journal of Energy Storage, 15, 172-180
Open this publication in new window or tab >>Influence of state-of-charge in commercial LiNi0.33Mn0.33Co0.33O2/LiMn2O4-graphite cells analyzed by synchrotron-based photoelectron spectroscopy
Show others...
2018 (English)In: Journal of Energy Storage, ISSN 2352-152X, Vol. 15, p. 172-180Article in journal (Refereed) Published
Abstract [en]

Degradation mechanisms in 26 Ah commercial Li-ion battery cells comprising graphite as the negative electrode and mixed metal oxide of LiMn2O4 (LMO) and LiNi1/3Mn1/3Co1/3O2 (NMC) as the positive electrode are here investigated utilising extensive cycling at two different state-of-charge (SOC) ranges, 10–20% and 60–70%, as well as post-mortem analysis. To better analyze these mechanisms electrochemically, the cells were after long-term cycling reassembled into laboratory scale “half-cells” using lithium metal as the negative electrode, and thereafter cycled at different rates corresponding to 0.025 mA/cm2 and 0.754 mA/cm2. The electrodes were also analyzed by synchrotron-based hard x-ray photoelectron spectroscopy (HAXPES) using two different excitation energies to determine the chemical composition of the interfacial layers formed at different depth on the respective electrodes. It was found from the extensive cycling that the cycle life was shorter for the cell cycled in the higher SOC range, 60–70%, which is correlated to findings of an increased cell resistance and thickness of the SEI layer in the graphite electrode as well as manganese dissolution from the positive electrode.

Keywords
Li-ion battery, Commercial cells, Battery ageing, Photoelectron spectroscopy
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-338184 (URN)10.1016/j.est.2017.11.010 (DOI)000426619500015 ()
Available from: 2018-01-08 Created: 2018-01-08 Last updated: 2019-04-11Bibliographically approved
Björklund, E., Brandell, D., Hahlin, M., Edström, K. & Younesi, R. (2017). How the Negative Electrode Influences Interfacial and Electrochemical Properties of LiNi1/3Co1/3Mn1/3O2 Cathodes in Li-Ion Batteries. Journal of the Electrochemical Society, 164(13), A3054-A3059
Open this publication in new window or tab >>How the Negative Electrode Influences Interfacial and Electrochemical Properties of LiNi1/3Co1/3Mn1/3O2 Cathodes in Li-Ion Batteries
Show others...
2017 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 164, no 13, p. A3054-A3059Article in journal (Refereed) Published
Abstract [en]

The cycle life of LiNi1/3Co1/3Mn1/3O2 (NMC) based cells are significantly influenced by the choice of the negative electrode. Electrochemical testing and post mortem surface analysis are here used to investigate NMC electrodes cycled vs. either Li-metal, graphite or Li4Ti5O12 (LTO) as negative electrodes. While NMC-LTO and NMC-graphite cells show small capacity fading over 200 cycles, NMC-Li-metal cell suffers from rapid capacity fading accompanied with an increased voltage hysteresis despite the almost unlimited access of lithium. X-ray absorption near edge structure (XANES) results show that no structural degradation occurs on the positive electrode even after >200 cycles, however, X-ray photoelectron spectroscopy (XPS) results shows that the composition of the surface layer formed on the NMC cathode in the NMC-Li-metal cell is largely different from that of the other NMC cathodes (cycled in the NMC-graphite or NMC-LTO cells). Furthermore, it is shown that the surface layer thickness on NMC increases with the number of cycles, caused by continuous electrolyte degradation products formed at the Li-metal negative electrode and then transferred to NMC positive electrode.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-338161 (URN)10.1149/2.0711713jes (DOI)000418409800021 ()
Funder
Swedish Energy Agency, 37725-1; 40495-1StandUp
Available from: 2018-01-08 Created: 2018-01-08 Last updated: 2019-04-11Bibliographically approved
Xu, C., Renault, S., Ebadi, M., Wang, Z., Björklund, E., Guyomard, D., . . . Gustafsson, T. (2017). LiTDI: A Highly Efficient Additive for Electrolyte Stabilization in Lithium-Ion Batteries. Chemistry of Materials, 29(5), 2254-2263
Open this publication in new window or tab >>LiTDI: A Highly Efficient Additive for Electrolyte Stabilization in Lithium-Ion Batteries
Show others...
2017 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 29, no 5, p. 2254-2263Article in journal (Refereed) Published
Abstract [en]

The poor stability of LiPF6-based electrolytes has always been a bottleneck for conventional lithium-ion batteries. The presence of inevitable trace amounts of moisture and the operation of batteries at elevated temperatures are particularly detrimental to electrolyte stability. Here, lithium 2trifluoromethy1-4,5-dicyanoimidazole (LiTDI) is investigated as a moisture-scavenging electrolyte additive and can sufficiently suppress the hydrolysis of LiPF6. With 2 wt % LiTDI, no LiPF6 degradation can be detected after storage for 35 days, even though the water level in the electrolyte is enriched by 2000 ppm. An improved thermal stability is also obtained by employing the LiTDI additive, and the moisture-scavenging mechanism is discussed. The beneficial effects of the LiTDI additive on battery performance are demonstrated by the enhanced capacity retention of both the LiNi1/3Mn1/3Co1/3O2 (NMC)/Li and NMC/graphite cells at 55 degrees C. In particular, the increase in cell voltage hysteresis is greatly hindered when LiTDI is presented in the electrolyte. Further development of the LiTDI additive may allow the improvement of elevated-temperature batteries, as well as energy savings by reducing the amount of effort necessary for dehydration of battery components.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2017
National Category
Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-319530 (URN)10.1021/acs.chemmater.6b05247 (DOI)000396639400040 ()
Funder
Swedish Energy Agency, 34191-1 39036-1Swedish Foundation for Strategic Research Carl Tryggers foundation StandUp
Available from: 2017-04-06 Created: 2017-04-06 Last updated: 2019-12-11
Björklund, E., Hahlin, M., Brandell, D., Edström, K. & Younesi, R. (2017). The influence of counter electrode on the capacity fading in LiNi0.33Mn0.33Co0.33O2-based Li-ion battery cells. In: : . Paper presented at Oorgandagarna 2017.
Open this publication in new window or tab >>The influence of counter electrode on the capacity fading in LiNi0.33Mn0.33Co0.33O2-based Li-ion battery cells
Show others...
2017 (English)Conference paper, Poster (with or without abstract) (Other academic)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-338218 (URN)
Conference
Oorgandagarna 2017
Available from: 2018-01-08 Created: 2018-01-08 Last updated: 2018-01-11Bibliographically approved
Björklund, E., Brandell, D., Hahlin, M., Edström, K. & Younesi, R. (2017). The influence of counter electrode on the capacity fading in LiNi0.33Mn0.33Co0.33O2-based Li-ion battery cells. In: : . Paper presented at Inorganic Chemistry Days (Oorgandagarna) 2017. Nynäshamn
Open this publication in new window or tab >>The influence of counter electrode on the capacity fading in LiNi0.33Mn0.33Co0.33O2-based Li-ion battery cells
Show others...
2017 (English)Conference paper, Poster (with or without abstract) (Other academic)
Place, publisher, year, edition, pages
Nynäshamn: , 2017
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-337509 (URN)
Conference
Inorganic Chemistry Days (Oorgandagarna) 2017
Funder
StandUp
Available from: 2017-12-30 Created: 2017-12-30 Last updated: 2018-01-12Bibliographically approved
Björklund, E., Wikner, E., Younesi, R., Wachtler, M., Brandell, D. & Edström, K. (2017). The influence of temperature and SOC ranges of ageing in commercial  LiNi0.33Mn0.33Co0.33O2/LiMn2O4-graphite commercial cells. In: : . Paper presented at International Conference on Advanced Lithium Batteries for Automobile Applications (ABAA-10).
Open this publication in new window or tab >>The influence of temperature and SOC ranges of ageing in commercial  LiNi0.33Mn0.33Co0.33O2/LiMn2O4-graphite commercial cells
Show others...
2017 (English)Conference paper, Poster (with or without abstract) (Other academic)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-338216 (URN)
Conference
International Conference on Advanced Lithium Batteries for Automobile Applications (ABAA-10)
Available from: 2018-01-08 Created: 2018-01-08 Last updated: 2018-01-11Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0002-2736-9145

Search in DiVA

Show all publications